JPH036272A - Pigment preparation - Google Patents
Pigment preparationInfo
- Publication number
- JPH036272A JPH036272A JP2115334A JP11533490A JPH036272A JP H036272 A JPH036272 A JP H036272A JP 2115334 A JP2115334 A JP 2115334A JP 11533490 A JP11533490 A JP 11533490A JP H036272 A JPH036272 A JP H036272A
- Authority
- JP
- Japan
- Prior art keywords
- pigment
- weight
- leather
- oligourethane
- pigment preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000049 pigment Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 71
- 239000010985 leather Substances 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 11
- 238000004040 coloring Methods 0.000 claims abstract description 9
- 239000004744 fabric Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 239000001023 inorganic pigment Substances 0.000 claims description 12
- 239000012860 organic pigment Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 abstract description 40
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 17
- 239000004408 titanium dioxide Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004056 anthraquinones Chemical class 0.000 abstract description 2
- 239000002562 thickening agent Substances 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000002542 deteriorative effect Effects 0.000 abstract 1
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 25
- 238000000576 coating method Methods 0.000 description 22
- 239000011248 coating agent Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- 229920002635 polyurethane Polymers 0.000 description 16
- 239000004814 polyurethane Substances 0.000 description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical class OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 12
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 239000011324 bead Substances 0.000 description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000002411 adverse Effects 0.000 description 5
- -1 butyl acetate Chemical compound 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000005442 diisocyanate group Chemical group 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000004848 polyfunctional curative Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- LHENQXAPVKABON-UHFFFAOYSA-N 1-methoxypropan-1-ol Chemical compound CCC(O)OC LHENQXAPVKABON-UHFFFAOYSA-N 0.000 description 2
- CUUNWWCQMKJKRR-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid;hexane-1,1-diol Chemical compound OCC(C)(C)CO.CCCCCC(O)O.OC(=O)CCCCC(O)=O CUUNWWCQMKJKRR-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 229960002380 dibutyl phthalate Drugs 0.000 description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical class O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910001385 heavy metal Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001034 iron oxide pigment Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920006264 polyurethane film Polymers 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- WGACMNAUEGCUHG-VYBOCCTBSA-N (2s)-2-[[(2s)-2-[[(2s)-2-acetamidopropanoyl]amino]propanoyl]amino]-n-[(2s)-6-amino-1-[[(2s)-1-[(2s)-2-[[(2s)-1-[[(2s)-5-amino-1-[[(2s)-1-[[(2s)-1-[[(2s)-6-amino-1-[[(2s)-1-amino-3-(4-hydroxyphenyl)-1-oxopropan-2-yl]amino]-1-oxohexan-2-yl]amino]-3-hydroxy- Chemical compound CC(=O)N[C@@H](C)C(=O)N[C@@H](C)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CO)C(=O)N[C@@H](CCCCN)C(=O)N[C@H](C(N)=O)CC1=CC=C(O)C=C1 WGACMNAUEGCUHG-VYBOCCTBSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- VUMCUSHVMYIRMB-UHFFFAOYSA-N 1,3,5-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1 VUMCUSHVMYIRMB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- VXKUOGVOWWPRNM-UHFFFAOYSA-N 3-ethoxypropyl acetate Chemical compound CCOCCCOC(C)=O VXKUOGVOWWPRNM-UHFFFAOYSA-N 0.000 description 1
- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 1
- OZCJSIBGTRKJGX-UHFFFAOYSA-N 4-methylcyclohexa-1,5-diene-1,4-diamine Chemical compound CC1(N)CC=C(N)C=C1 OZCJSIBGTRKJGX-UHFFFAOYSA-N 0.000 description 1
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- KYIMHWNKQXQBDG-UHFFFAOYSA-N N=C=O.N=C=O.CCCCCC Chemical compound N=C=O.N=C=O.CCCCCC KYIMHWNKQXQBDG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940067573 brown iron oxide Drugs 0.000 description 1
- 239000001058 brown pigment Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 150000001845 chromium compounds Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000000109 continuous material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 229940035690 di-n-octyl sodium sulfosuccinate Drugs 0.000 description 1
- 229940100539 dibutyl adipate Drugs 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229940105994 ethylhexyl acetate Drugs 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 108010074544 myelin peptide amide-12 Proteins 0.000 description 1
- MZYHMUONCNKCHE-UHFFFAOYSA-N naphthalene-1,2,3,4-tetracarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=C(C(O)=O)C(C(O)=O)=C21 MZYHMUONCNKCHE-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C11/00—Surface finishing of leather
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/32—Material containing basic nitrogen containing amide groups leather skins
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Coloring (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、顔料調製物及びその皮革及び皮革布の仕上げ
剤(dressing agents)の着色に対する
使用法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigment preparations and their use for the coloring of leather and leather fabric dressing agents.
皮革及びポリウレタン又は水に不溶なセルロースエステ
ルに基づく皮革布に対する水に不溶な仕上げ剤の、顔料
調製物を用いる着色は公知である。The coloring of water-insoluble finishes for leather and leather fabrics based on polyurethanes or water-insoluble cellulose esters using pigment preparations is known.
この目的のために使用される顔料調製物は、主に顔料及
び通常の添加剤例えば溶媒のほかに、コロジオン、酢酸
セルロース、アセト酪酸セルロース、エチルセルロース
又はポリ塩化ビニル−ポリ酢酸ビニル共重合体に基づく
顔料結合剤を、可塑剤例えばフタル酸ジブチルを添加し
て又は添加せずに含んでなる。これらの顔料調製物は、
皮革及び皮革模造品の仕上げ剤の性質に及びその最終製
品の性質にしばしば悪影響を及ぼす。一方でそれは皮革
又は皮革模造品を硬くし、その濡れ及び乾燥折り曲げ強
度を減じ、そしてその耐低温性を屓う。Pigment preparations used for this purpose are mainly based on collodion, cellulose acetate, cellulose acetobutyrate, ethyl cellulose or polyvinyl chloride-polyvinyl acetate copolymers, in addition to the pigment and the usual additives such as solvents. A pigment binder is included with or without the addition of a plasticizer such as dibutyl phthalate. These pigment preparations are
The properties of the finishes on leather and leather imitations and the properties of their final products are often adversely affected. On the one hand, it stiffens the leather or leather imitation, reduces its wet and dry bending strength, and reduces its low temperature resistance.
他方でそれは滲出する。特に光堅牢性及び熱の影響下に
おける黄変又は接着は公知の組成物成分によって悪影響
を受ける。On the other hand, it exudes. In particular, light fastness and yellowing or adhesion under the influence of heat are adversely affected by known composition components.
これらの欠点を克服する試みは、皮革の仕上げ剤組成物
における又は皮革布の被覆における結合剤として使用さ
れる如きものと同一の又は同様のポリウレタンを顔料結
合剤として用いることによって行なわれてきた。この方
法では、言及した欠点はいくらか軽減される。しかしな
がら例えばポリウレタンが互いに及びコロジオン及び他
のセルロース誘導体と非常に限られた程度でしか適合し
ないから、各仕上げ剤組成物に対して正確に均衡のとれ
た顔料調製物を用いることが必要である。Attempts to overcome these drawbacks have been made by using polyurethanes identical or similar to those used as binders in leather finishing compositions or as binders in leather fabric coatings as pigment binders. In this way, the mentioned disadvantages are somewhat alleviated. However, since, for example, polyurethanes are only compatible to a very limited extent with each other and with collodion and other cellulose derivatives, it is necessary to use precisely balanced pigment preparations for each finish composition.
斯くして、いずれの皮革及び皮革布の仕上げ剤に対して
用いるのにも普遍的に適当であり且つ更に公知の顔料調
製物の欠点を含まない顔料調製物の必要性が生じてきた
。仕上げ剤又はコーティング組成物中に重合又は混合に
よって導入された結合剤を有する調製物は特に好適であ
る。A need has thus arisen for a pigment preparation which is universally suitable for use in any leather and leather fabric finishing and which, furthermore, does not have the disadvantages of the known pigment preparations. Preparations with binders introduced by polymerization or admixture into the finishing or coating composition are particularly suitable.
本発明は、A)無機及び/又は有機顔料、B)液体オリ
ゴウレタン、及び適当な場合にはC)顔料調製物に通常
の1種又はそれ以上の添加剤、を含んでなり、但しA)
:B)の重量比がl二0゜1〜50である顔料調製物に
関する。The invention comprises A) an inorganic and/or organic pigment, B) a liquid oligourethane, and, if appropriate, C) one or more additives conventional in pigment preparations, with the exception that A)
:B) in a weight ratio of 120°1 to 50.
顔料は好ましくはオリゴウレタン中に分散せしめられる
。The pigment is preferably dispersed in the oligourethane.
好適な調製物は、A)有機顔料2〜60重量%、特に好
ましくは5〜30重量%、又は無機顔料2〜80重量%
、特に好ましくは10〜65重量%、B)オリゴウレタ
ン5〜98重量%、及びC)添加剤特に溶媒5〜90重
量%、特に好ましくは8〜30重量%を含んでなる、但
しA)+B)+C)が合計で100重量%である調製物
である。Suitable preparations include: A) 2 to 60% by weight of organic pigments, particularly preferably 5 to 30% by weight, or 2 to 80% by weight of inorganic pigments;
, particularly preferably from 10 to 65% by weight, B) from 5 to 98% by weight of an oligourethane, and C) from 5 to 90% by weight, particularly preferably from 8 to 30% by weight of an additive, especially a solvent, with the exception that A)+B )+C) totaling 100% by weight.
好適なオリゴウレタンは立体障害された又は保護された
イソシアネート基を有する。適用条件下に他の存在する
重合体と反応しうるオリゴウレタンは非常に特に好適で
ある。Suitable oligourethanes have sterically hindered or protected isocyanate groups. Very particular preference is given to oligourethanes which can react with other polymers present under the conditions of application.
適当な場合には、顔料調製物は通常の添加物例えば溶媒
、増量剤又は増粘剤を含有しうる。If appropriate, the pigment preparations may contain customary additives such as solvents, fillers or thickeners.
適当な溶媒はアルコール例えばイソブタノール、シクロ
ヘキサノール、tert−ブタノール、ジアセトンアル
コール、エチルグリコール、グリコールモノメチルエー
テル、ケトン例えばメチルエチルケトン、シクロヘキサ
ノン、エステル例えば酢酸ブチル、7タル酸エステル例
えばフタル酸ジメチル、フタル酸ジブチル、フタル酸ジ
オクチル、燐酸エステル例えばトリクレジルホスフェー
ト、アジピン酸エステル例えばアジピン酸ジブチル、ア
ルキルスルホン酸エステル例えばフェニル又はトリルペ
ンタデカンスルホネート、即ち例えば−般にニトロセル
ロース又はPVCの可塑性化に公知の生成物、或いはメ
トキシグロビル又はエトキシプロピルアセテート、或い
は酸アミド例えばジメチルホルムアミド又はメチルピロ
リドン、及びいくつかの炭化水素例えばベンゼン、トル
エン又はキシレンである。シクロヘキサノン、ジメチル
ホルムアミド又はメトキシプロピルアセテートは好適で
ある。Suitable solvents are alcohols such as isobutanol, cyclohexanol, tert-butanol, diacetone alcohol, ethyl glycol, glycol monomethyl ether, ketones such as methyl ethyl ketone, cyclohexanone, esters such as butyl acetate, heptathalic acid esters such as dimethyl phthalate, dibutyl phthalate. , dioctyl phthalate, phosphoric acid esters such as tricresyl phosphate, adipate esters such as dibutyl adipate, alkylsulfonate esters such as phenyl or tolyl pentadecane sulfonate, i.e. products generally known for the plasticization of nitrocellulose or PVC, or methoxyglobil or ethoxypropyl acetate, or acid amides such as dimethylformamide or methylpyrrolidone, and some hydrocarbons such as benzene, toluene or xylene. Cyclohexanone, dimethylformamide or methoxypropyl acetate are preferred.
120°C以上の沸点の溶媒は特に好適である。Solvents with a boiling point above 120°C are particularly suitable.
OH又はNH基を含まない溶媒は好適に使用される6特
別な具体例において、用いる「溶媒」は例えばPVCの
可塑性化に通常のもの、即ち基材中に残留し且つ蒸発に
よって除去する必要のない溶媒である。Solvents that do not contain OH or NH groups are preferably used.6 In a special embodiment, the "solvent" used is, for example, one that is customary for the plasticization of PVC, i.e. one that remains in the substrate and has to be removed by evaporation. There is no solvent.
顔料調製物は、常法により化合物を通常の湿式粉砕装置
、例えばローター−ステーターミル、ビーズミル、又は
ボールミル中で分散させることによって製造しうる。分
散された顔料の粒径は0゜2〜2μであるべきである。The pigment preparations may be prepared in conventional manner by dispersing the compounds in conventional wet milling equipment, such as rotor-stator mills, bead mills, or ball mills. The particle size of the dispersed pigment should be between 0°2 and 2μ.
本発明に従って顔料調製物中に導入される顔料は制限が
ない。それは有機型又は無機型であってよい。適当な有
機顔料の例は、アゾ、アンスラキノン、アゾポルフィン
、チオインジゴ、ジオキサジン、ナフタレンテトラカル
ボン酸又はペリレンテトラカルボン酸系の顔料並びにレ
ーキ形の染料例えばスルホン酸及び/又はカルボン酸基
を含む染料のCa、Mg又はAQレーキである。これら
の多くは例えばカラーインデックス(Colour I
ndex)第2版から公知である。適当な無機顔料の例
は硫化亜鉛、硫化カドミウム又はセレン化カドミウム、
ウルトラマリン、二酸化チタン、酸化鉄、ニッケル又は
クロムの化合物並びにカーボンブラックである。There are no restrictions on the pigments that are introduced into the pigment preparation according to the invention. It may be of organic or inorganic type. Examples of suitable organic pigments are pigments based on azo, anthraquinone, azoporphine, thioindigo, dioxazine, naphthalenetetracarboxylic acid or perylenetetracarboxylic acid, and lake-type dyes, such as dyes containing sulfonic and/or carboxylic acid groups. , Mg or AQ lake. Many of these are, for example, color indexes (Colour I
ndex) 2nd edition. Examples of suitable inorganic pigments are zinc sulphide, cadmium sulphide or cadmium selenide,
Ultramarine, titanium dioxide, iron oxide, nickel or chromium compounds as well as carbon black.
適当なオリゴウレタンは分子量5000〜50000の
ものである。分子量10000〜50000のものは好
適であり、分子量15000〜40000のものは特に
好適である。黄変しない或いは酸素、光、熱又は水によ
って分解しないオリゴウレタンは非常に特に好適である
。Suitable oligourethanes have a molecular weight of 5,000 to 50,000. Those with a molecular weight of 10,000 to 50,000 are preferred, and those with a molecular weight of 15,000 to 40,000 are particularly preferred. Very particular preference is given to oligourethanes which do not yellow or decompose due to oxygen, light, heat or water.
現在入手しうるポリエステル、ポリエーテル、ポリカー
ボネート、ポリエーテルエステル、イソシアネート及び
グリコール及び/又はアミンに基づく延鎖剤はポリウレ
タンの製造に使用しうる。Currently available chain extending agents based on polyesters, polyethers, polycarbonates, polyether esters, isocyanates and glycols and/or amines can be used in the production of polyurethanes.
アジピン酸、コハク酸、ゲルタール酸、炭酸、フタル酸
、テレフタル酸、イソフタル酸、モノ、ジ、トリ及びポ
リエチレングリコール又はモノ、ジ、トリ及びポリプロ
ピレングリコール、ブタンジオール、ヘキサンジオール
、ポリカプロラクトン、これらの酸及びグリコールの互
いの及びアミノ基を含むポリオールとの混合物から得ら
れるポリエステルは好適に使用される。アジピン酸、7
タル酸及び炭酸のエステルは好適に使用される。Adipic acid, succinic acid, geltaric acid, carbonic acid, phthalic acid, terephthalic acid, isophthalic acid, mono, di, tri and polyethylene glycol or mono, di, tri and polypropylene glycol, butanediol, hexanediol, polycaprolactone, these acids Polyesters obtained from mixtures of polyols and glycols with each other and with polyols containing amino groups are preferably used. Adipic acid, 7
Esters of tarric acid and carbonic acid are preferably used.
公知の方法によりアミノ化された又はされてないアルコ
ールで開始しうるエチレングリコール、プロピレングリ
コール、ブタンジオール(これらは混合物としても存在
しうる)に基づくポリニーチルは単独で又はエーテルと
組合せて使用しうる。Polyneedle based on ethylene glycol, propylene glycol, butanediol (which can also be present as a mixture) which can be started with alcohols aminated or non-aminated by known methods can be used alone or in combination with ethers.
オリゴウレタンの製造には本質的にいずれのポリイソシ
アネートも適当である。ポリイソシアネート例えば重合
した又は重合してないトルイレンジフェニルジイソンア
ネート又はメチレンジフェニルジイソシアネート又はヘ
キサンジイソシアネート又はインフオロンジイソシアネ
ートは好適に使用される。脂肪族イソシアネートは高度
に光堅牢性であるが故に特に好適である。得られるオリ
ゴウレタンはOH末端の、イソシアネート末端の、又は
末端保護された形で存在しうる。Essentially any polyisocyanate is suitable for the production of oligourethanes. Polyisocyanates such as polymerized or unpolymerized tolylene diphenyl diisonanate or methylene diphenyl diisocyanate or hexane diisocyanate or influorone diisocyanate are preferably used. Aliphatic isocyanates are particularly preferred because they are highly lightfast. The resulting oligourethanes can be present in OH-terminated, isocyanate-terminated or end-capped form.
オリゴウレタンは好ましくは立体障害された遊離の又は
保護されたイソシアネート基を含む。The oligourethane preferably contains sterically hindered free or protected isocyanate groups.
本発明に従って使用されるオリゴウレタンは好適にはN
CO: OH比〉1で製造される。The oligourethane used according to the invention is preferably N
Produced at a CO:OH ratio>1.
適当な末端基保護剤は1級、2級又は3級のアルコール
又はオキシム、例えばブタノンオキシムである。Suitable end-group protecting agents are primary, secondary or tertiary alcohols or oximes, such as butanone oxime.
顔料調製物を用いる条件下において、保護されたイソシ
アネート基は遊離し、次いで例えばコーティング組成物
、コーティング、又は皮革の仕上げ剤と反応でき、従っ
てその性質を改善する。Under the conditions using the pigment preparation, the protected isocyanate groups are liberated and can then react with, for example, the coating composition, coating or leather finish, thus improving its properties.
本発明による顔料調製物によって着色しうる有機皮革仕
上げ剤は、例えば独国特許公報第1,174.937号
及び第1,278.064号に開示されている。本発明
の顔料調製物を用いれば、有機溶媒に溶解する殆んどい
ずれの結合剤も着色しうる。これらは芳香族及び脂肪族
ポリウレタン1成分系並びにアミン含有2成分系の着色
に及びセルロース誘導体に基づくフェス、例えば皮革又
は皮革代用品の仕上げに用いるものに特に適当である。Organic leather finishing agents which can be colored with the pigment preparations according to the invention are disclosed, for example, in DE 1,174,937 and DE 1,278,064. Almost any binder that is soluble in organic solvents can be colored using the pigment preparations of the invention. They are particularly suitable for the coloring of aromatic and aliphatic polyurethane one-component systems as well as amine-containing two-component systems and for use in finishing surfaces based on cellulose derivatives, such as leather or leather substitutes.
顔料調製物の選択は所望の色の効果に応じて行なわれる
。高い隠ぺい力が所望ならば、無機顔料を含んでなる調
製物を用いる。一方処理した基材が高光沢の透明色を期
待するならば、有機顔料を含んでなる調製物を使用する
。更に顔料と関連した堅牢性例えば光堅牢性及び移動堅
牢性、耐熱性などにも注目する。The choice of pigment preparation is made depending on the desired color effect. If high hiding power is desired, preparations comprising inorganic pigments are used. On the other hand, if the treated substrate is expected to have a high gloss transparent color, preparations comprising organic pigments are used. Furthermore, attention is paid to the fastness properties associated with the pigments, such as light fastness, transport fastness, heat resistance, etc.
これらの新規な顔料は反応性ポリウレタン系例えば独国
特許公報第3.309.992号の2成分法において或
いは所謂高固体系(独国特許公報第3.239.900
号による)において用いるものに使用するのに特に適当
である。立体障害された又は保護されたイソシアネート
を有するオリゴウレタンを組成物成分として用いる具体
例はこの適用形に対して特に適当である。適用条件下に
、組成物成分は反応性コーティング生成物と反応する。These new pigments can be used in reactive polyurethane systems, for example in the two-component process of DE 3.309.992, or in so-called high solids systems (DE 3.239.900).
Particularly suitable for use in applications (according to No. 1). Embodiments using oligourethanes with sterically hindered or protected isocyanates as composition components are particularly suitable for this application. Under application conditions, the composition components react with the reactive coating product.
斯くして組成物成分は強くコーティング中に導入される
。The composition components are thus strongly incorporated into the coating.
公知の顔料調製物に対比して、本発明による顔料調製物
は、それが非常に簡単に製造でき、汎用性であり、着色
すべき仕上げ剤及び基材に悪影響せず、そして特に顔料
と関連した堅牢性を損わないという利点を有する。−4
0〜+25°Cの軟化点を有するオリゴウレタンは特に
好適である。乾燥炉において存在していてよいいずれか
の溶媒の蒸発後、それらはその有機溶媒中溶液から連続
したいずれのフィルムも形成しない。驚くコトに、それ
らは粘着性を感じたり、貧弱な熱耐摩耗性を有する仕上
げ剤組成物を提供しない。また仕上げ剤組成物は良好な
耐低温性と良好な濡れ及び乾燥折り曲げ強度も有する。In contrast to the known pigment preparations, the pigment preparation according to the invention is characterized by the fact that it is very easy to produce, is versatile, does not have an adverse effect on the finishes and substrates to be colored, and is especially suitable for pigments. It has the advantage of not impairing its robustness. -4
Oligourethanes with a softening point of 0 to +25°C are particularly suitable. After evaporation of any solvent that may be present in the drying oven, they do not form any continuous film from their solution in organic solvent. Surprisingly, they do not provide finish compositions that feel tacky or have poor heat abrasion resistance. The finish composition also has good low temperature resistance and good wet and dry bending strength.
更にそれらはコーティング及び仕上げ側糸から移動しな
い。溶媒の代りにアジピン酸エステル又はフタル酸エス
テル形の可塑剤を添加すれば、いずれかの硬化を妨げる
。これらの生成物を、コーティング剤に基づいて30%
以下、好ましくは10%以下の量で用いる場合、これら
の化合物は移動しない。Moreover, they do not migrate from the coating and finishing side threads. Adding plasticizers in the form of adipate or phthalate esters instead of solvents will prevent curing of either. 30% of these products based on the coating agent.
Hereinafter, when used in an amount of preferably 10% or less, these compounds do not migrate.
セルロース又はポリ酢酸ビニルに基づく結合剤を含んで
なる顔料調製物を用いれば、異なる顔料の混合物の場合
、しばしば、特に有機顔料の浮上(float ing
)が起こる。これは本発明による顔料調製物を用いて防
ぐことができ、そして種々のコーティング剤との適合性
は最適な程度まで改善され、この結果それは顔料結合剤
、例えば織物の捺染に用いるものに対して汎用的に使用
することができる。With pigment preparations comprising binders based on cellulose or polyvinyl acetate, it is often possible to improve the floating of organic pigments, especially in the case of mixtures of different pigments.
) occurs. This can be prevented using the pigment preparation according to the invention, and the compatibility with various coating agents is improved to an optimal extent, so that it is compatible with pigment binders, such as those used for printing textiles. Can be used for general purposes.
下記の実施例は本発明を例示する:
1、オリゴウレタンの製造
実施例・1.2
保護されたイソシアネート基を有するオリゴウレタンを
本実施例に記述する:
63〜70(7)OH価(OH2000ミリモル)を有
するヘキサンジオールネオペンチルグリコールアジペー
ト1600gを減圧下に完全に脱水し、次いで4Qの撹
拌しているビーカー中においてイン7オロンジイソシア
ネート444g (N00400089モル)及びトリ
イソシアナトへキシルビウレット80g (NC020
0ミリモル)と、理論値のNCO値が達成されるまで(
即ち約360升間)90〜lOO°Cで反応させた。次
いで反応混合物をブタノンオキシム240g(2760
ミリモル)で更に処理し、反応を更に200分撹拌しな
がら90〜100℃で進行させた。次いで混合物の濃度
をフタル酸ジ−n−ブチルで70%まで調節した。この
結果25℃で2’2000mPa5の粘度を有する保護
されたイソシアネート基2.80%を有するオリゴウレ
タンヲ得た。The following examples illustrate the present invention: 1. Example for the preparation of oligourethanes 1.2 Oligourethanes with protected isocyanate groups are described in this example: 63-70 (7) OH number (OH2000 1600 g of hexanediol neopentyl glycol adipate with 1 mmol) are completely dehydrated under reduced pressure and then in a 4Q stirred beaker 444 g of in7olone diisocyanate (N00400089 mol) and 80 g of triisocyanatohexylbiuret (NC020
0 mmol) until the theoretical NCO value is achieved (
That is, about 360 liters) was reacted at 90-100°C. The reaction mixture was then mixed with 240 g (2760 g) of butanone oxime.
mmol) and the reaction was allowed to proceed for an additional 200 minutes at 90-100°C with stirring. The concentration of the mixture was then adjusted to 70% with di-n-butyl phthalate. As a result, an oligourethane containing 2.80% of protected isocyanate groups and a viscosity of 2'2000 mPa5 at 25° C. was obtained.
実施例1.2
63〜70のOH価(oH2000ミリモル)を有する
ヘキサンジオールネオペンチルグリコールアジペート1
600gを減圧下に完全に脱水し、次いで4Qの撹拌し
ているビーカー中においてイン7オロンジイソシアネー
ト444g (N00400089モル)及びトリイソ
シアナトへキシルビウレット809 (NC0200
ミリモル)と、理論値のNCO値が達成されるまで(即
ち約360分間)90〜100°Cで反応させた。次い
で反応混合物をブタノンオキシム240g(2760ミ
リモル)で更に処理し、反応を更に200分撹拌しなが
ら90〜lOO°Cで進行させt;。次いで混合物の濃
度をメトキシプロピルアセテートで70%まで調節した
。この結果25°Cで230Q mPa5の粘度を有す
る保護されたイソシアネート基2,80%を有するオリ
ゴウレタンを得た。実施例1.3
56のOH価(OH2000ミリモル)を有するポリプ
ロピレングリコールエーテル20009を減圧下に完全
に脱水し、次いで4I2の撹拌しているビーカー中にお
いてへキサメチレンジイソシアネート354i+ (
NCO420’Oミリモル)と、理論値のNCO値が達
成されるまで(即ち約300分間)90−100°Cで
反応させた。次いで反応混合物をブタノンオキシム24
0g(2760ミリモル)で更に処理し反応を、更に2
00分撹拌しながら90〜100°Cで進行させた。次
いで混合物の濃度をメトキシプロピルアセテートで70
%まで調節した。この結果25℃で200m P a
sの粘度ををする保護されたイソシアネート基2.70
%を有するオリゴウレタンを得た。Example 1.2 Hexanediol neopentyl glycol adipate 1 with an OH number of 63-70 (oH 2000 mmol)
600 g are completely dehydrated under reduced pressure and then in a 4Q stirred beaker 444 g of in7olone diisocyanate (N00400089 mol) and triisocyanatohexyl biuret 809 (NC0200
mmol) at 90-100°C until the theoretical NCO value was achieved (i.e. approximately 360 minutes). The reaction mixture was then further treated with 240 g (2760 mmol) of butanone oxime and the reaction was allowed to proceed for a further 200 minutes at 90-100° C. with stirring. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate. This resulted in an oligourethane containing 2.80% of protected isocyanate groups with a viscosity of 230 Q mPa5 at 25°C. Example 1.3 Polypropylene glycol ether 20009 with an OH number of 56 (2000 mmol OH) is completely dehydrated under reduced pressure and then added to hexamethylene diisocyanate 354i+ (
NCO (420'O mmol) was reacted at 90-100°C until the theoretical NCO value was achieved (i.e. approximately 300 minutes). The reaction mixture was then diluted with butanone oxime 24
The reaction was further treated with 0 g (2760 mmol).
The mixture was allowed to proceed at 90-100°C with stirring for 00 minutes. The mixture was then brought to a concentration of 70% with methoxypropyl acetate.
Adjusted to %. As a result, 200mPa at 25℃
The protected isocyanate group has a viscosity of s 2.70
% was obtained.
実施例1.4
56のOH価(OH2000ミリモル)を有するヘキサ
ンジオールポリカーボネート20009を減圧下に完全
に脱水し、次いで4Qの撹拌しているビーカー中におい
てイン7オロンジイソシアネート444g(NGO40
00ミリモル)及びトリイソシアナトへキシルビウレッ
ト809(NGO200ミリモル)と、理論値のNc。Example 1.4 Hexanediol polycarbonate 20009 with an OH number of 56 (2000 mmol OH) was completely dehydrated under reduced pressure and then 444 g of in7olone diisocyanate (NGO40
00 mmol) and triisocyanatohexylbiuret 809 (NGO 200 mmol) and the theoretical Nc.
値2.67%が達成されるまで(即ち約360分間)9
0〜100℃で反応させた。次いで混合物の濃度をメト
キシプロピルアセテートで70%まで調節した。次いで
イソシアネート基及び25°Cテ1300mPa5の粘
度を有するウレタンを得た。9 until a value of 2.67% is achieved (i.e. approximately 360 minutes)
The reaction was carried out at 0 to 100°C. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate. A urethane having isocyanate groups and a viscosity of 1300 mPa5 at 25° C. was then obtained.
実施例1.5
56のOH価(OH2000ミリモル)を有するポリプ
ロピレングリコールエーテル20009を減圧下に完全
に脱水し、次いで4αの撹拌しているビーカー中におい
て2.4/2.6−ジイソシアナート−1−メチルベン
ゼン1839(NGO2100ミリモル)及びヘキサメ
チレンジイソシアネート176g (NcO2100ミ
IJモル)と、理論値のNCO値が達成されるまで(即
ち約200分間)90〜100℃で反応させた。次いで
反応混合物をブタノンオキシム2409 (2760
ミリモル)で更に処理し、反応を更に120分撹拌しな
がら90〜100℃で進行させた。次いで混合物の濃度
をメトキシプロピルアセテートで70%まで調節した。Example 1.5 Polypropylene glycol ether 20009 with an OH number of 56 (2000 mmol OH) is completely dehydrated under reduced pressure and then mixed with 2.4/2.6-diisocyanate in a stirred beaker at 4α. 1839 mmol of 1-methylbenzene (2100 mmol of NGO) and 176 g of hexamethylene diisocyanate (2100 mmol of NcO) were reacted at 90-100 DEG C. until the theoretical NCO value was achieved (ie about 200 minutes). The reaction mixture was then converted to butanone oxime 2409 (2760
(mmol) and the reaction was allowed to proceed for an additional 120 minutes at 90-100° C. with stirring. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate.
この結果25°Cで3 Q Q mPa5の粘度を有す
る保護されたイソシアネート基2,68%を有するオリ
ゴウレタンを得tこ 。This resulted in an oligourethane containing 2.68% of protected isocyanate groups with a viscosity of 3 Q Q mPa5 at 25°C.
実施例1.6
63〜70のOH価(OH2000ミリモル)を有する
ヘキサンジオールネオペンチルグリコールアジベート1
600gを減圧下に完全に脱水し、次いで4Qの撹拌し
ているビーカー中において1.3.5−トリイソプロピ
ルベンゼン2.4−ジイソシアネート(立体障害された
もの)61Og (NCO4200ミリモル)と、理論
値のNCO値が達成されるまで(即ち約300分間)9
0〜100″Cで反応させた。次いで反応混合物をブタ
ノンオキシム240g(2760ミリモル)で更に処理
し、反、応を、更に200分撹拌しながら90〜100
℃で進行させた。次いで混合物の濃度をメトキシプロピ
ルアセテートで70%まで調節した。この結果25°C
で3800 mPa5の粘度を有する保護されたイソシ
アネート基2.60%を有するオリゴウレタンヲ得た。Example 1.6 Hexanediol neopentyl glycol adipate 1 with an OH number of 63-70 (2000 mmol OH)
600 g were completely dehydrated under reduced pressure and then 61 O g (4200 mmol NCO) of 1,3,5-triisopropylbenzene 2,4-diisocyanate (sterically hindered) in a 4Q stirred beaker, theoretical until an NCO value of 9 is achieved (i.e. approximately 300 minutes).
The reaction mixture was then further treated with 240 g (2760 mmol) of butanone oxime and the reaction was heated at 90-100"C with stirring for an additional 200 minutes.
Proceed at °C. The concentration of the mixture was then adjusted to 70% with methoxypropyl acetate. As a result, 25°C
An oligourethane containing 2.60% of protected isocyanate groups with a viscosity of 3800 mPa5 was obtained.
2、顔料調製物の製造
実施例2.1
実施例1.1からの顔料結合剤1.8kgを7タル酸ジ
ーn−ブチル1.7kgで希釈し、二酸化チタン顔料[
バイエルチタン(Bayertitan■)RFK−2
]6.5kgを添加し、そして混合物を、可溶化機を用
いて15分間200 Orpmで撹拌した。2. Preparation of Pigment Preparation Example 2.1 1.8 kg of the pigment binder from Example 1.1 are diluted with 1.7 kg of di-n-butyl 7-talate to form a titanium dioxide pigment [
Bayer titan RFK-2
]6.5 kg were added and the mixture was stirred for 15 minutes at 200 Orpm using a solubilizer.
次いでこれをボールミル中で粉砕し、十分分散した顔料
ペーストを得た。This was then ground in a ball mill to obtain a well-dispersed pigment paste.
実施例2.2
実施例1.2からの顔料結合剤1.8kgをメトキシプ
ロピルアセテート85g及びトリメチルベンゼンの混合
物(ESSOからのツルペッツ1100)85で希釈し
、二酸化チタン顔料[バイエルチタンRFDII 6.
5kgを添加し、そして混合物を、可溶化機を用いて1
5分間200 Orpmで撹拌した。次いでこれをビー
ズミル中で粉砕し、十分分散した顔料ペーストを得た。Example 2.2 1.8 kg of the pigment binder from Example 1.2 are diluted with 85 g of methoxypropyl acetate and a mixture of trimethylbenzene (Zurpetz 1100 from ESSO) and added to the titanium dioxide pigment [Beyer Titanium RFDII 6.
5 kg and the mixture was mixed using a solubilizer for 1
Stir at 200 Orpm for 5 minutes. This was then ground in a bead mill to obtain a well-dispersed pigment paste.
実施例2.3
実施例1.3からの顔料結合剤2.0kgをメトキシプ
ロピルアセテート6.99kg及びトリエタノールアミ
ン109で希釈し、次いでカーボンブラック・モナ、−
チ(Monarch@) 800 [カポット(Cab
ot)製]1.0kgを添加し、そして混合物を可溶化
機を用いて2000 rpmで20分間撹拌した。次い
でカーボンブラック分散液を、必要とされる黒色の深さ
と隠ぺい力が達成されるまで、直径1mmのガラスピー
ズを用いるビーズミル中において冷却しなからl又は2
回粉砕した。Example 2.3 2.0 kg of pigment binder from Example 1.3 are diluted with 6.99 kg of methoxypropyl acetate and 109 kg of triethanolamine and then carbon black Mona, -
Monarch @ 800 [Cab
ot)] was added, and the mixture was stirred for 20 minutes at 2000 rpm using a solubilizer. The carbon black dispersion is then cooled and heated in a bead mill using 1 mm diameter glass beads until the required black depth and hiding power are achieved.
It was crushed twice.
実施例2.4
実施例1.6からの顔料結合剤1.95kgをメトキシ
プロピルアセテート1.3kg及びツルペッツ100
(ESSO製)1.2kgで希釈し、褐色の酸化鉄顔料
645T型(バイエル社製)5.5kgを添加し、そし
て混合物を可溶化機を用いて2000rp+nで15分
間撹拌した。次いでこの暗褐色の顔料分散液を、必要と
される色の深さと隠ぺい力が達成されるまで、直径1.
mmのガラスピーズを用いるビーズミル中において冷却
しなから1又は2回粉砕した。Example 2.4 1.95 kg of pigment binder from Example 1.6 was combined with 1.3 kg of methoxypropyl acetate and Tsurpetz 100
(manufactured by ESSO), 5.5 kg of brown iron oxide pigment type 645T (manufactured by Bayer AG) were added and the mixture was stirred for 15 minutes at 2000 rpm+n using a solubilizer. This dark brown pigment dispersion is then applied in a 1.5 mm diameter until the required depth of color and hiding power is achieved.
It was ground once or twice before cooling in a bead mill using mm glass beads.
他の無機顔料を用いて同一の粘度の顔料ペーストを製造
するためには、各特別な顔料に対して顔料:結合剤比及
び溶媒を決定することが必要であつl;。In order to produce pigment pastes of the same viscosity with other inorganic pigments, it is necessary to determine the pigment:binder ratio and solvent for each particular pigment.
実施例2.5
実施例1.5からの顔料結合剤2.6kgをメトキシプ
ロピルアセテート5.7kgで希釈し、ノボバーム(N
ovoperm■)レッドF5RK(ヘキスト社製)1
.7kgを添加し、そして混合物を可溶化機を用いて2
000 rpmで20分間撹拌した。次いで顔料分散液
を、必要とされる色の深さと光沢が達成されるまで、直
径1mmのガラスピーズを用いるビーズミル中において
冷却しなから1又は2回粉砕した。Example 2.5 2.6 kg of pigment binder from Example 1.5 are diluted with 5.7 kg of methoxypropyl acetate and Novobalm (N
ovoperm ■) Red F5RK (manufactured by Hoechst) 1
.. 7 kg and the mixture was solubilized using a solubilizer.
Stirred at 000 rpm for 20 minutes. The pigment dispersion was then milled once or twice without cooling in a bead mill using 1 mm diameter glass beads until the required depth of color and gloss was achieved.
実施例2.6
実施例1.4からの顔料結合剤2 、2 kgをメトキ
シプロピルアセテート6.0kgで希釈し、バリオゲン
(Paliogen@)レッド−バイオレットに498
5(BASF製)1.8kgを添加し、混合物を可溶化
機を用いて2000 rpmで20分間撹拌した。次い
で顔料分散液を、必要とされる色の深さと光沢が達成さ
れるまで、直径1mmのガラスピーズを用いるビーズミ
ル中において冷却しなからl又は2回粉砕した。Example 2.6 2.2 kg of the pigment binder from Example 1.4 is diluted with 6.0 kg of methoxypropyl acetate to give 498 kg of Paliogen@ Red-Violet.
5 (manufactured by BASF) was added, and the mixture was stirred for 20 minutes at 2000 rpm using a solubilizer. The pigment dispersion was then ground one or two times without cooling in a bead mill using 1 mm diameter glass beads until the required depth of color and gloss was achieved.
ノボバーム・レッドF5R5及びバリオゲン・レッド−
バイオレットに4985の代りに、他の有機顔料を用い
て、同様に有用な顔料調製物を製造した。同一の粘度の
顔料ペーストを得るためには、実施例2.1.2.2及
び2.4の無機顔料の場合に記述したように、各特別な
有機顔料に対する顔料:結合剤比及び溶媒を決定するこ
とが必要であった。Novobalm Red F5R5 and Variogen Red-
Similarly useful pigment preparations were made using other organic pigments in place of 4985 for violet. To obtain pigment pastes of the same viscosity, the pigment:binder ratio and solvent for each particular organic pigment should be adjusted as described for the inorganic pigments in Examples 2.1.2.2 and 2.4. It was necessary to decide.
アセトブチレートワニス(実施例3.1の適用を参照)
又はコロジオンワニス(実施例3.2及び3.3の適用
を参照)又はポリウレタン溶液(実施例3.4〜3.1
4の適用を参照)の着色のために、これらの顔料調製物
を単独で或いは実施例2.1及び2,2に記述した二酸
化チタン顔料調製物、カーボンブラック顔料調製物(実
施例2゜3)、又は実施例2.4の無機顔料調製物と組
合せて用いた。Acetobutyrate varnish (see application example 3.1)
or collodion varnishes (see applications of Examples 3.2 and 3.3) or polyurethane solutions (Examples 3.4 to 3.1)
These pigment preparations can be used alone or in combination with the titanium dioxide pigment preparations described in Examples 2.1 and 2, 2, the carbon black pigment preparations (see Applications in Example 2.3). ), or in combination with the inorganic pigment preparation of Example 2.4.
すべての顔料ペーストは、フロック化及び浮遊なしに互
いに良く混和しえた。それ故に沈降、色すじ又は変色は
逆転コーティング(reversecoat ing)
において起こらなかった。この顔料調製物によって作ら
れる色相はすべての場合に良く再現できた。All pigment pastes were well miscible with each other without flocculation and floating. Therefore, sedimentation, color streaks or discoloration are reverse coated.
It didn't happen in. The hues produced by this pigment preparation were well reproduced in all cases.
3、着色
実施例3.1
セルロースアセトブチレートぐブチリル含量49%、2
0%アセトン溶液の20°Cでの粘度約20Pas)
25g、フタル酸ジ−n−ブチル5g、ステアリン酸n
−ブチル4g、ポリエーテルシロキサン(独国公開特許
第3,244.955号の実施例1に従って製造)2g
、2−エチルヘキシルアセテート1049、メトキシプ
ロパツール410g及び酢酸n−ブチル410gからな
る溶液に、実施例2.1からの二酸化チタン調製物40
gを添加した。5分間の撹拌後、容易に噴霧でさ且つ極
めて隠ぺい力を有するそのまま使用しうる白色の塗料を
得た。これは光堅牢性、アミン堅牢性及び170℃まで
耐黄変性を示した。この塗料は磨かれt;及び完全にき
めのよい皮革の強い隠ぺい力の白色仕上げ剤として特に
適当であった。3. Coloring Example 3.1 Cellulose acetobutyrate butyryl content 49%, 2
Viscosity of 0% acetone solution at 20°C is approximately 20 Pas)
25g, di-n-butyl phthalate 5g, stearic acid n
- 4 g of butyl, 2 g of polyether siloxane (prepared according to Example 1 of DE 3,244,955)
, 1049 of 2-ethylhexyl acetate, 410 g of methoxypropanol and 410 g of n-butyl acetate, 40 g of the titanium dioxide preparation from Example 2.1.
g was added. After stirring for 5 minutes, a ready-to-use white paint was obtained which was easily sprayable and had excellent hiding power. It exhibited light fastness, amine fastness and yellowing resistance up to 170°C. This paint was particularly suitable as a high-hidden white finish on polished and perfectly textured leather.
実施例3.2
エステル可溶性コロジオンウール(ブタノールで付湿、
65%、標準形9E)329、フタル酸ジ−n−ブチル
40g、ヒマシ油159.2−エチルヘキシルアセテー
ト50g及び酢酸ブチル8139からなる溶液に、実施
例2.3からのカーポンプチック調製物509を撹拌し
ながら添加した。5分間撹拌した後、空気圧噴霧ガンを
用いて噴霧しうる強い黒色のコロジオン塗料を得た。こ
れは磨かれた且つ完全にきめのよい皮革の高光沢仕上げ
剤として特に適当であった。Example 3.2 Ester-soluble collodion wool (wetted with butanol,
65%, standard form 9E) 329, 40 g of di-n-butyl phthalate, castor oil 159. Added with stirring. After stirring for 5 minutes, a strong black collodion paint was obtained which could be sprayed using a pneumatic spray gun. It was particularly suitable as a high gloss finish for polished and perfectly textured leather.
実施例3.2
エステル可溶性コロジオンウール(ブタノールで付湿、
65%、標準形15E)53g、フタル酸ジ−n−ブチ
ル24g、ヒマシ油4g、ステアリン酸ブチル8g、2
−エチルヘキシルアセテート−ブチルI 8 5g、ト
リエタノールアミン2g、スルホコハク酸ジーnーオク
チルナトリウム159、エチレンオキシド約20モルの
、ノニルフェノール1モルへの付加物12gからなる溶
液に、実施例2.3からのカーボンブラック調製物50
9を撹拌しながら添加した。顔料分散液を良く分散させ
た後、混合物を水525gで乳化させI;。Example 3.2 Ester-soluble collodion wool (wetted with butanol,
65%, standard form 15E) 53g, di-n-butyl phthalate 24g, castor oil 4g, butyl stearate 8g, 2
The carbon from Example 2.3 is added to a solution consisting of 5 g of butyl I -ethylhexyl acetate, 2 g of triethanolamine, 159 g of di-n-octyl sodium sulfosuccinate, 12 g of the adduct of about 20 mol of ethylene oxide to 1 mol of nonylphenol. black preparation 50
9 was added with stirring. After the pigment dispersion was well dispersed, the mixture was emulsified with 525 g of water.
得られた水で希釈しうる黒色乳化液は、熱可塑的に仕上
げた、磨かれた且つ完全にきめのよい皮革に対する強い
黒色の仕上げ剤として非常に適当であった。The resulting water-dilutable black emulsion was highly suitable as a strong black finish for thermoplastically finished, polished and perfectly textured leather.
実施例3,4 ポリウレタン樹脂(独国公開特許第2.4.23。Examples 3 and 4 Polyurethane resin (German Published Patent No. 2.4.23).
764号に従って製造)80g、tert−ブタノール
130g、トルエン100g、トリメチルベンゼンの混
合物[ESSOからのツルペッツ(Solvesso’
) l 0 0] 2 5 0g、アセト酪酸セルロー
ス(ブチリル含量49%、20%アセトン溶液の20°
Cでの粘度2 0Pas) 2 79 、ポリエーテル
シロキサン(独国公開特許第3.2 4 4,955号
の実施例2Aに従って製造)3g、メチルエチルケトン
1009及びメトキシプロパツール260gからなる溶
液に実施例2.4からの酸化鉄調製物50gを撹拌しな
がら添加した。最終の塗料をエアレス・スプレーガンで
噴霧したが、非常に良好な流出性を示し、皮革又は皮革
模造品に適用した時家具用皮革に対する良好な隠ぺい性
仕上げとして特に適当である光沢をもつ非常に柔軟な褐
色の仕上げを与えた。764), 130 g of tert-butanol, 100 g of toluene, trimethylbenzene [Solvesso' from ESSO
) l 0 0] 2 5 0 g, cellulose acetobutyrate (butyryl content 49%, 20° of 20% acetone solution)
Example 2 was added to a solution consisting of 3 g of polyethersiloxane (prepared according to example 2A of DE 3.244.955), methyl ethyl ketone 1009 and 260 g of methoxypropanol. 50 g of the iron oxide preparation from .4 were added with stirring. The final paint was sprayed with an airless spray gun and had a very good sheen with very good run-off and which is particularly suitable as a good hiding finish on furniture leather when applied to leather or leather imitations. It gave a soft brown finish.
実施例3.5
織物のコーティングに用いる顔料混入ポリウレタン溶液
を、実施例2.2からの顔料調製物から次のように製造
した;
実施例2.2からの二酸化チタン顔料調製物89を、ポ
リウレタン25g、ジメチルホルムアミド45ao2及
びメチルエチルケトン30mQからなる溶液に、高速撹
拌機を用いて200〜3 0 0 rpmで撹拌しなが
ら添加した。3〜5分間撹拌した後、逆転法(reve
rsal process)による織物のコーティング
に非常に適当である安定な顔料分散液を得た。公知の手
法に従い、本方法で織物上に形成されたポリウレタンフ
ィルムは均一であり、スポットを含まなかった。使用し
たI成分ポリウレタンは、アジピン酸及びヘキサンジオ
ール/ネオペンチルグリコールから得られる平均分子量
500〜3000のポリエステル及びジフェニルメタン
4、4′−ジイソシアネートから製造され、統いてブタ
ンジオールと反応させた。Example 3.5 A pigmented polyurethane solution for coating textiles was prepared from the pigment preparation from Example 2.2 as follows; Titanium dioxide pigment preparation 89 from Example 2.2 was 25 g, 45 ao2 of dimethylformamide and 30 mQ of methyl ethyl ketone was added to a solution consisting of 25 ao2 of dimethylformamide and 30 mQ of methyl ethyl ketone while stirring at 200-300 rpm using a high speed stirrer. After stirring for 3-5 minutes, reverse the
A stable pigment dispersion was obtained which is highly suitable for coating textiles by the rsal process. In accordance with known techniques, the polyurethane film formed on the fabric with this method was uniform and free of spots. The component I polyurethane used was prepared from a polyester with an average molecular weight of 500 to 3000 obtained from adipic acid and hexanediol/neopentyl glycol and diphenylmethane 4,4'-diisocyanate, which was reacted together with butanediol.
実施例3.6
メチルエチルケトン5gを、末端OH基を有する架橋し
うるポリウレタン30g及び酢酸エチル709からなる
溶液に添加し、次いで実施例2。Example 3.6 5 g of methyl ethyl ketone are added to a solution consisting of 30 g of crosslinkable polyurethane with terminal OH groups and 709 ethyl acetate, then Example 2.
2からの二酸化チタン顔料調製物8gを、200〜3
0 0 rpmの高速撹拌下に添加した。3〜5分の撹
拌後、トリメチロールプロパン1モル及びトルイレンジ
イソシアネート3モルを反応させることによって製造し
たポリイソシアネート及び促進剤として重金属塩を添加
して、逆転法又は直接法による織物のコーティングに適
当である安定な顔料分散液を得た。公知の方法に従い、
本方法で形成したポリウレタンは均一で、スポットを含
まなかった。8 g of titanium dioxide pigment preparation from 200 to 3
Addition was made under high speed stirring at 0.00 rpm. After stirring for 3 to 5 minutes, a polyisocyanate prepared by reacting 1 mol of trimethylolpropane and 3 mol of toluylene diisocyanate and a heavy metal salt as promoter is added, suitable for coating textiles by the inverse method or by the direct method. A stable pigment dispersion was obtained. According to known methods,
The polyurethane formed by this method was uniform and free of spots.
実施例3.7
英国特許筒1.418.550号に従って製造した30
%脂肪族ポリカーボネート−ポリウレタン尿素100g
を、実施例2.5からの本発明による顔料li製物15
9と機械的に撹拌しながら混合し、この混合物を、静置
ドクターブレード又は同様の公知の塗布具を用いてエン
ボス加工したシリコーン剥離紙に適用した。被覆量は固
体30g/m!であった。Example 3.7 30 manufactured according to British Patent No. 1.418.550
% aliphatic polycarbonate-polyurethaneurea 100g
is the pigment li product 15 according to the invention from Example 2.5.
9 with mechanical agitation and the mixture was applied to embossed silicone release paper using a stationary doctor blade or similar known applicator. Coverage amount is 30g/m of solids! Met.
80〜125℃に加熱した乾燥炉を通過させ、次いで冷
却した後、これの隠ぺい力を同様の方法で製造した他の
顔料調製物のそれと比較した。本発明による粉砕した顔
料のペーストは良好な隠ぺい力を有した。After passing through a drying oven heated to 80-125°C and then cooling, its hiding power was compared with that of other pigment preparations produced in a similar manner. The paste of ground pigment according to the invention had good hiding power.
実施例3.8
実施例3.7に記述した上塗りは不適当であり、従って
25000 mPa5/ 25°Cの粘度を有するDM
F:MEK 50:50中の更なる芳香族ポリウレタ
ン樹脂を適用しなければならなかった。被覆量は固体5
0g /m”であった。このポリウレタン樹脂は分子量
2000のポリプロピレングリコールエーテル2000
g、■、4−ブタンジオール200g及び4.4 ’−
ジフェニルメタンジイソシアネート800gから製造し
た。Example 3.8 The topcoat described in Example 3.7 is unsuitable and therefore DM with a viscosity of 25000 mPa5/25 °C
Further aromatic polyurethane resin in F:MEK 50:50 had to be applied. Coverage amount is solid 5
The polyurethane resin was polypropylene glycol ether 2000 with a molecular weight of 2000.
g, ■, 200 g of 4-butanediol and 4.4'-
Prepared from 800 g of diphenylmethane diisocyanate.
色を付与するために、実施例2.5からの本発明による
顔料調製物20gを完全に混入した。To impart color, 20 g of the pigment preparation according to the invention from Example 2.5 were mixed in completely.
実施例3.9
独国公開特許第2.902.090号の実施例1に従っ
て製造した保護されたNGOプレポリマー10009、
実施例2.3からの粉砕した顔料ペーストloOg、3
,3′−ジメチル−4,4′−ジアミノジシクロヘキシ
ルメタン900gを、同時に40℃に加熱しながら減圧
下に混合した。Example 3.9 Protected NGO prepolymer 10009 prepared according to Example 1 of DE 2.902.090,
Milled pigment paste loOg from Example 2.3, 3
, 3'-dimethyl-4,4'-diaminodicyclohexylmethane were mixed under reduced pressure while simultaneously heating to 40°C.
被覆量、固体200g/m!。架橋温度150〜160
°C0上述した保護されたNCOプレポリマーを、ジア
ミンの添加によりアンカー(anchor)コーティン
グとして用いた。実施例2.3からの粉砕した顔料ペー
スト50g及び40%ポリウレタン樹脂分散液200g
及び水溶性シリコーン油30gを分散剤と共に完全に混
合した。Coverage amount: 200g/m of solids! . Crosslinking temperature 150-160
The protected NCO prepolymer described above was used as an anchor coating by addition of diamine. 50 g of ground pigment paste from Example 2.3 and 200 g of 40% polyurethane resin dispersion
and 30 g of water-soluble silicone oil were thoroughly mixed with the dispersant.
室温での長い貯蔵寿命を有するこのペーストを、エンボ
ス加工した剥離紙に又はシリコーンマトリックスに又は
連続スチール細片に直接使用した。This paste, which has a long shelf life at room temperature, was used directly on embossed release papers or on silicone matrices or on continuous steel strips.
すべてのこれらの−時的な基材は上述した生成物又は他
の化学品(例えばアクリレート)からなる1種又はそれ
以上のコーティングを塗布することができた。生成物は
公知の塗布具(ドクターブレード、スプレーガン、ロー
ラーなど)で適用した。All these temporary substrates could be coated with one or more coatings consisting of the products mentioned above or other chemicals (eg acrylates). The products were applied with known applicators (doctor blade, spray gun, roller, etc.).
直ぐ後に連続的な材料例えば織布、編布、フリース及び
凝固布(coagulatsd fabric)を積層
にしてローラーで適」した。この積層にした材料を、種
々の材料(金属、ゴム、紙基材の積層物、フオーム)か
らなるローラー中を通過させ、次いで熱循環空気で13
0〜270℃に加熱しt:乾燥炉を通過させl;。Immediately thereafter, continuous materials such as woven, knitted, fleece and coagulated fabrics were layered and applied with a roller. This laminated material is passed through rollers made of various materials (metal, rubber, paper-based laminates, foam) and then heated for 13 minutes with heated circulating air.
Heat to 0-270°C and pass through a drying oven.
乾燥機のから出口において材料をローラー上で冷却し、
再使用しうる分離可能な担持体(carrier)から
剥した。cooling the material on rollers at the exit from the dryer;
It was removed from a reusable separable carrier.
実施例3.10
実施例2.1〜2.6に示しt;顔料調製物は逆転法に
よる皮革のコーティングに使用しうる2成分ポリウレタ
ンの着色に非常に適当であった。本方法は次の通りであ
った:
p−トルイレンジアミン200gをメチルエチルケトン
800gに撹拌しながら5分間かけて溶解した。この黄
褐色の溶液に顔料調製物2.4の200gを添加した。Example 3.10 The pigment preparations shown in Examples 2.1 to 2.6 were very suitable for coloring two-component polyurethanes which can be used for coating leather by the inversion process. The method was as follows: 200 g of p-tolylenediamine was dissolved in 800 g of methyl ethyl ketone over 5 minutes with stirring. 200 g of pigment preparation 2.4 were added to this tan solution.
この顔料調製物は水で希薄であったけれど、それは数週
間の貯蔵寿命を宵し、ポリイソシアネートとの反応後に
逆転法で皮革をコーティングするのに非常に適当であっ
た。公知の方法によるこの工程で製造されたポリウレタ
ンフィルムは均一でスポットがなかった。用いたポリイ
ソシアネートはp’−トルイレンジイソシアネートを、
アジピン酸、テレフタル酸及びジエチレングリコールか
ら製造される分子量1000〜3000のポリエステル
と反応させることによって製造した。Although this pigment preparation was dilute with water, it had a shelf life of several weeks and was very suitable for coating leather in the inversion process after reaction with polyisocyanates. Polyurethane films produced by this process according to known methods were uniform and spot-free. The polyisocyanate used was p'-toluylene diisocyanate,
It was produced by reacting with a polyester having a molecular weight of 1,000 to 3,000 produced from adipic acid, terephthalic acid and diethylene glycol.
実施例3.II
プレポリマーA(下記参照)342g (NGO262
ミリモル)を、例えば米国特許第4.31O,493号
に記述されている如く2成分混合スプレーガンを用いて
、コーティングライン上でジアミンコーティング剤溶液
4259 (250ミリモル)で処理した。硬化剤溶
液の組成は次の通りであった:
酢酸エチル
2800部
実施例2.4に従って
処理した酸化鉄顔料
50s
理想式
%式%
[式中、mは27〜35の整数及びRはエチレン及びプ
ロピレン基J
のポリエーテルポリシロキサン 150 gス
プリット・レザー(split 1eather) 、
平織布、フリース及び不織布を、例えば米国特許第4.
310,493号に記述されているようにポリウレタン
樹脂用のスプレーガンを用いる逆転法によってコーティ
ングすることができた。このスプレーガン機は、主成分
としてのズレポリマー用の加熱された貯蔵容器、硬化剤
調製物用の貯蔵容器、硬化剤用及びプレポリマー用の秤
量具、並びに米国特許第4.310.493号に記述さ
れている如き成分の混合及び噴霧のための2成分ポリウ
レタンスプレーガン、プレポリマーの加熱しうる入口、
硬化剤の入口、溶媒の入口、及び圧縮空気の入口からな
った。Example 3. II Prepolymer A (see below) 342g (NGO262
(mmol) was treated with diamine coating solution 4259 (250 mmol) on the coating line using a two-component mix spray gun as described, for example, in U.S. Pat. No. 4,310,493. The composition of the hardener solution was as follows: 2800 parts of ethyl acetate 50s of iron oxide pigment treated according to Example 2.4 Ideal formula % Formula % where m is an integer from 27 to 35 and R is ethylene and 150 g split leather of propylene group J polyether polysiloxane,
Plain woven fabrics, fleeces and non-woven fabrics are described, for example, in US Pat.
310,493, by an inversion method using a spray gun for polyurethane resins. This spray gun machine includes a heated storage container for the shear polymer as the main component, a storage container for the curing agent preparation, a weighing device for the curing agent and for the prepolymer, and U.S. Pat. No. 4,310,493. a two-component polyurethane spray gun for mixing and atomizing the components as described in , a heatable inlet of the prepolymer;
It consisted of a curing agent inlet, a solvent inlet, and a compressed air inlet.
プレポリマーを加熱しうる貯蔵容器に入れ、その粘度を
低下させるt;めに50〜80℃まで加熱した。硬化剤
調製物を適当な容器中に入れた。プレポリマー及び硬化
剤調製物を、秤量具を備えた別々の導管を通してスプレ
ーガンに供給した。この供給量はNCO: NH3の当
量比において1゜00=1〜1.75:1で変化させた
。塗布量は可変であり、所望のフィルムの厚さ及び単位
時間当りに塗布すべき面積に依存した。反応混合物の成
分は、米国特許第4.310.493号に詳細にお述さ
れている如き2成分ポリウレタン・スプレーガンの混合
空間及び混合管において最短の可能な時間内で完全に混
合され、そして圧縮空気により出口ノズルから吐出され
た。成分の反応は一度に、すでに混合過程で起った。The prepolymer was placed in a heatable storage container and heated to 50-80°C to reduce its viscosity. The curing agent preparation was placed in a suitable container. The prepolymer and curing agent formulations were fed to the spray gun through separate conduits equipped with weighing devices. The feed rate was varied in the equivalent ratio of NCO:NH3 from 1°00=1 to 1.75:1. The coating rate was variable and depended on the desired film thickness and the area to be coated per unit time. The components of the reaction mixture are thoroughly mixed within the shortest possible time in the mixing space and mixing tube of a two-component polyurethane spray gun as detailed in U.S. Pat. No. 4,310,493, and Compressed air was expelled from the outlet nozzle. The reaction of the components took place at once, already during the mixing process.
ガンの出口において、混合物は圧縮空気(作用圧3〜6
kg/ cm” )の作る空気の渦で更に混合され、
噴霧の三角錐形から広い流れに変換される。At the outlet of the gun, the mixture is exposed to compressed air (working pressure 3-6
kg/cm”) is further mixed by the air vortex created by the
The triangular pyramid shape of the spray is transformed into a wide stream.
ガンはシリコーンゴムで被覆された(天然ゴムの感覚を
もつ)マトリックス上に又は他の別の担持体上にm15
0crnで約25〜30@/分の速度で通過した。別の
キャリヤはガンの下を横切って、2〜10m/分の速度
で移動した。マトリックス又は別々の担体上に噴霧され
る材料はフィルムに流出し、混合物の粘度は増大し、そ
して噴霧操作の開始から約30〜90秒後に材料はペー
スト状になった。スプリット・レザー又は他の物質を、
反応材料上又は中に置いてプレスした。次いで全コーテ
ィングを、60〜120°Cに加熱された乾燥炉中を通
過させた。噴霧操作の開始から約3〜6分後に、コーテ
ィングはマトリックス又は分離可能な担持体から粘着性
なく剥がしえた。The gun is mounted on a matrix coated with silicone rubber (with the feel of natural rubber) or on another separate carrier.
It passed at a speed of about 25-30 @/min at 0 crn. Another carrier moved underneath the gun at a speed of 2-10 m/min. The material sprayed onto the matrix or separate carrier ran out into a film, the viscosity of the mixture increased and the material became pasty about 30-90 seconds after the start of the spraying operation. split leather or other materials,
Placed on or in the reaction material and pressed. The entire coating was then passed through a drying oven heated to 60-120°C. Approximately 3-6 minutes after the start of the spraying operation, the coating could be peeled off from the matrix or separable carrier without tack.
ポリウレタン尿素フィルムは0.15〜0.45mmの
厚さであった。The polyurethaneurea film was 0.15-0.45 mm thick.
このコーティングした平たい材料は、天然皮革と区別で
きないきめを有し、短時間後に乾燥し、例えば現代の製
靴業によってff層し且つ加工することができた。コー
ティングとスプリット−レザー間の接着は漫秀で、手触
りは心良い乾きと軟かさがあった。This coated flat material had a texture indistinguishable from natural leather, dried after a short time and could be ff-layered and processed, for example, by the modern shoe industry. The adhesion between the coating and the split leather was excellent, and the feel was pleasantly dry and soft.
実施例3.12
プレポリマーB(下記を参照)4749 (NC04
00ミリモル)を、実施例3.11と同一の方法のコー
ティング・ラインにおいで下記の硬化剤溶液130gで
処理した:
2.4−1−ルイレンジアミン 400g
メチルエチルケトン 6009
本発明による上述の顔料懸濁液2.5 400g
実施例3.11による流れ調節剤 1009
驚くことに、種々の生成物のこの懸濁液を、機械的撹拌
により長期間にわたって懸濁させつづけることは必ずし
も・必要のないことが発見された。Example 3.12 Prepolymer B (see below) 4749 (NC04
00 mmol) was treated with 130 g of the following hardener solution in a coating line in the same manner as Example 3.11: 2.4-1-Lylene diamine 400 g
Methyl ethyl ketone 6009
2.5 400 g of the above pigment suspension according to the invention
Flow control agent according to Example 3.11 1009
Surprisingly, it has been found that it is not necessary to keep this suspension of the various products suspended for long periods of time by mechanical stirring.
これらの条件下において、顔料分散液は通常沈降する傾
向があるが、これは本発明による分散液の場合には起こ
らなかった。本発明による顔料調製物は、機械的撹拌が
不必要であって、空気泡が入ってこないから、即ち気泡
が硬化しt;フィルム中に存在しないから、更に有利で
あった。機械的に撹拌されてないプレポリマー及び硬化
剤溶液から製造される平らな担体上のコーティングは、
密なフィルム、即ち空気の内包が少ないから強度の高め
られたフィルムが特色である。Under these conditions pigment dispersions usually tend to settle, but this did not occur in the case of the dispersions according to the invention. The pigment preparation according to the invention was further advantageous because no mechanical stirring was required and no air bubbles were introduced, ie air bubbles were not present in the cured film. Coatings on flat supports made from prepolymer and hardener solutions that are not mechanically stirred are
It is characterized by a dense film, that is, a film with increased strength because it contains less air.
機械的撹拌機を備えた容器を介して得られるフィルムと
比較して、得られたフィルム又はコーティングは次の性
質を有した。Compared to the film obtained via a vessel equipped with a mechanical stirrer, the obtained film or coating had the following properties:
容器
撹拌機あり 撹拌機なし
引張り強度 10 MPa 12 )
JPa破断伸張 440% 500%耐
引裂き伝播性 22 daN 24 da
N実施例3.13
プレポリマー〇(下記参照)640g (888ミリモ
ル)を硬化剤調製物582gと良く混合し、分離しうる
担持体上に注いだ。Container with stirrer Without stirrer Tensile strength 10 MPa 12)
JPa breaking elongation 440% 500% tear propagation resistance 22 daN 24 da
N Example 3.13 640 g (888 mmol) of Prepolymer 〇 (see below) were mixed well with 582 g of hardener preparation and poured onto a separable support.
この硬化剤調製物は次の組成に相当した:実施例2.5
からの顔料調製物 120g用いたI PD
A l 709(1モル〕のうち、a)12.9モル
%は遊離のIPDMとして存在し、
b)41.6モル%は
として存在し、
c)45.5モル%は混合物中のIPDMのビス(メチ
ルエチルケトン)ケチミンとして存在し lこ。This curing agent preparation corresponded to the following composition: Example 2.5
I PD using 120 g of pigment preparation from
Of the Al 709 (1 mol), a) 12.9 mol% is present as free IPDM, b) 41.6 mol% is present as, and c) 45.5 mol% is present as free IPDM. It exists as bis(methyl ethyl ketone) ketimine.
(組成はガスクロマトグラフィーにより混合物の分析か
ら計算した。)
更に混合物は反応水及び更なる13gの追加量の合計か
ら計算される水37.9gを全部で含有した。、(ケチ
ミン基のアミノ基への加水分解的開裂に理論的に必要と
される水の量は24.9gであった。)硬化剤混合物の
NH2当量は6009であった。(The composition was calculated from the analysis of the mixture by gas chromatography.) In addition, the mixture contained a total of 37.9 g of water, calculated from the sum of the reaction water and a further 13 g of addition. (The amount of water theoretically required for the hydrolytic cleavage of the ketimine group to the amino group was 24.9 g.) The NH2 equivalent weight of the curing agent mixture was 6009.
実施例3.14
実施例2.3からのカーボンブラック調製物は冷塗布法
による皮革の捺染に対する2成分ポリウレタンの着色に
非常に適当であった。Example 3.14 The carbon black preparation from Example 2.3 was highly suitable for coloring two-component polyurethanes for leather printing by the cold application method.
低度の分岐と末端○H基を有する架橋しうるポリエステ
ル709、酢酸エチル30g、酢酸ブチル209、シク
ロへキサノン20g及び酢酸メチルグリコール109か
らなる溶液に、カーボンブラック調製物15gを高速撹
拌機で200〜300 rpn+下に撹拌しながら添加
した。5分間撹拌した後、安定な顔料分散液を得た。こ
れはトリメチロールプロパン1モル及び]・ルイレンジ
イソシアネート3モルを反応させることによって製造し
たポリイソシアネート41g及び促進剤としての重金属
を添加した後、冷塗布工程による皮革の捺染に適当であ
った。公知の方法に従い、この方法で製造される捺染し
た皮革は均一に着色し、スポットがなかった。この黒色
は華麗であり、高光沢を有した。用いたポリエステルは
アジピン酸、ジエチレングリコール及びトリメチロール
プロパンから製造され、1000〜3000の平均分子
量を有しt二。15 g of the carbon black preparation was added to a solution consisting of 709 crosslinkable polyester with a low degree of branching and terminal ○H groups, 30 g of ethyl acetate, 209 butyl acetate, 20 g of cyclohexanone and 109 methyl glycol acetate using a high-speed stirrer. Added with stirring under ~300 rpm+. After stirring for 5 minutes, a stable pigment dispersion was obtained. After adding 41 g of a polyisocyanate prepared by reacting 1 mol of trimethylolpropane and 3 mol of lylene diisocyanate and heavy metals as promoters, it was suitable for printing leather by a cold coating process. According to known methods, the printed leather produced in this way was uniformly colored and free of spots. The black color was brilliant and had a high gloss. The polyester used was made from adipic acid, diethylene glycol and trimethylolpropane and had an average molecular weight of 1000-3000.
実施例3.15
独国持許公報第2.801,817号、7〜8頁、3行
の実施例1に従って製造した顔料調製物は単独で適用す
るのに最も適していた。しかしながら、すべて同一の顔
料結合剤を用いて製造した有機顔料の無機顔料との混合
物は一定の機械的撹拌なしには均一に混合されないまま
であることが示された。特に調製済み溶液を長期間放置
した後、特に重い方の無機顔料の沈降及び特に軽い方の
有機顔料の浮上が観察できた。Example 3.15 The pigment preparation prepared according to Example 1 of German Patent Application No. 2.801,817, pages 7-8, line 3, was most suitable for application alone. However, it has been shown that mixtures of organic pigments with inorganic pigments, all made using the same pigment binder, do not remain homogeneously mixed without constant mechanical stirring. Particularly after the prepared solution was allowed to stand for a long period of time, sedimentation of particularly heavy inorganic pigments and floating of particularly light organic pigments could be observed.
実施例3,16
コロジオン顔料調製物を含んでなる最終調製物は、例え
ば皮、織布、織物などによって表わされるような軟材料
に対して用いるのに限られた程度でしか適当でなかった
。Examples 3, 16 The final preparations comprising the collodion pigment preparations were only suitable to a limited extent for use on soft materials, such as those represented by leather, woven fabrics, fabrics, and the like.
可塑剤を添加して又は添加しないでコロジオンを組成物
剤として用いる顔料調製物は、軟質の仕上げ剤例えばポ
リウレタンに基づくもの、例えば皮革及び皮革模造品の
性質に悪影響を示した。長期の貯蔵後、それは皮革又は
皮革模造品を硬くし、感触及びきめを損ない、折り曲げ
強度を減じ、そして耐低温性を損なった。光堅牢性及び
熱及びアミンの影響下での黄変並びに接着はとりわけこ
れらの顔料調製物によって悪影響を受ける。Pigment preparations using collodion as a composition agent with or without the addition of plasticizers have shown an adverse effect on the properties of soft finishes such as those based on polyurethane, such as leather and leather imitations. After long-term storage, it hardens the leather or leather imitation, impairs feel and texture, reduces bending strength, and impairs low temperature resistance. Lightfastness and yellowing under the influence of heat and amines as well as adhesion are particularly adversely affected by these pigment preparations.
4、実施例3.11〜3.13に対するNCOプレポリ
マーの製造
プレポリマーA
アジピン酸、ヘキサンジオール及びネオペンチルグリコ
ールから得られるヒドロキシル価64(OH73,5当
量)の60部を、llo’cの圧力溶液中で1時間にわ
たり水を除去し、そしてトルエン18.2部の存在下に
トルイレンジイソシアネート(2,4−異姓体80%及
び2.6=異性体20%、147当量)12.8部と1
.10°Cで反応させて、NGO含量3.2%のプレポ
リマーを製造した。この粘度は20℃で4000 mP
a5及び70℃で500 mPa5であった。4. Preparation of NCO prepolymers for Examples 3.11 to 3.13 Prepolymer A 60 parts of hydroxyl number 64 (OH73.5 equivalents) obtained from adipic acid, hexanediol and neopentyl glycol were added to llo'c. Water was removed in a pressure solution for 1 hour and 12.8 toluylene diisocyanate (80% 2,4-isomer and 2.6 = 20% isomer, 147 equivalents) in the presence of 18.2 parts of toluene part and 1
.. The reaction was carried out at 10°C to produce a prepolymer with an NGO content of 3.2%. This viscosity is 4000 mP at 20°C
a5 and 500 mPa5 at 70°C.
プレポリマーB
アジピン酸及びエチレングリコール(0,53モル)か
ら製造したポリエステル500gから、13トール及び
110°Cで1時間にわたり水を除去した。次いでこの
ポリエステルを110°Cで6時間4.4′−ジイソシ
アナトジフェニルメタン(NC01,06モル)132
.5gと反応させた。Prepolymer B Water was removed from 500 g of polyester prepared from adipic acid and ethylene glycol (0.53 mol) at 13 torr and 110° C. for 1 hour. This polyester was then heated at 110°C for 6 hours with 132 4'-diisocyanatodiphenylmethane (NC01.06 mol).
.. It was reacted with 5g.
NGO含量3.54%のプレポリマーを得た。A prepolymer with an NGO content of 3.54% was obtained.
プレポリマーC
エチレンオキシド50重量%及びプロピレンオキシド5
0重量%から(l、2−プロピレングリコールで開始)
得たヒドロキシル価56の線状ポリエーテル100g及
びプロピレンオキシド27.5重量%及びエチレンオキ
シド72.5重量%から(グリセロールで開始)得たO
HHSO33官能性ポリエーテル10009を、脱水し
、そいて4.4′−ジフェニルメタンジイソシアネート
666gと90℃で反応させた。反応時間は45分、N
GO含量は5.8%、そして当量は724りであった。Prepolymer C 50% by weight of ethylene oxide and 5% of propylene oxide
From 0% by weight (starting with l, 2-propylene glycol)
O obtained (starting with glycerol) from 100 g of the obtained linear polyether with a hydroxyl number of 56 and 27.5% by weight of propylene oxide and 72.5% by weight of ethylene oxide.
HHSO33 functional polyether 10009 was dehydrated and reacted with 666 g of 4,4'-diphenylmethane diisocyanate at 90°C. Reaction time was 45 minutes, N
The GO content was 5.8% and the equivalent weight was 724.
Claims (1)
タン、及び適当な場合にはC)顔料調製物に通常の1種
又はそれ以上の添加剤、を含んでなり、但しA):B)
の重量比が1:0.1〜50である顔料調製物。 2、A)有機顔料2〜60重量%、B)オリゴウレタン
5〜98重量%、及びC)添加剤、特に溶媒5〜90重
量%を含んでなり、但しA)+B)+C)が合計で10
0重量%である特許請求の範囲第1項記載の顔料調製物
。 3、A)有機顔料5〜30重量%、B)オリゴウレタン
5〜98重量%、及びC)添加剤、特に溶媒8〜90重
量%を含んでなり、但しA)+B)+C)が合計で10
0重量%である特許請求の範囲第1項記載の顔料調製物
。 4、A)無機顔料2〜80重量%、B)オリゴウレタン
5〜98重量%、及びC)添加剤、特に溶媒5〜90重
量%を含んでなり、但しA)+B)+C)が合計で10
0重量%である特許請求の範囲第1項記載の顔料調製物
。 5、A)無機顔料10〜65重量%、B)オリゴウレタ
ン5〜98重量%、及びC)添加剤、特に溶媒8〜90
重量%を含んでなり、但しA)+B)+C)が合計で1
00重量%である特許請求の範囲第1項記載の顔料調製
物。 6、オリゴウレタンの分子量が5000〜50000で
ある特許請求の範囲第1〜5項の何れかに記載の顔料調
製物。 7、オリゴウレタンの分子量が15000〜40000
である特許請求の範囲第1〜5項の何れかに記載の顔料
調製物。 8、オリゴウレタンが立体障害されたイソシアネート基
を有する特許請求の範囲第1〜7項の何れかに記載の顔
料調製物。 9、オリゴウレタンが保護されたイソシアネート基を有
する特許請求の範囲第1〜8項の何れかに記載の顔料調
製物。 10、特許請求の範囲第1〜9項の何れかに記載の顔料
調製物を、皮革の着色及び皮革布の仕上げ剤に対して使
用すること。Claims: 1. Comprising: 1. A) an inorganic and/or organic pigment, B) a liquid oligourethane, and, if appropriate, C) one or more additives customary for pigment preparations. , but A):B)
A pigment preparation having a weight ratio of 1:0.1 to 50. 2. A) 2-60% by weight of an organic pigment, B) 5-98% by weight of an oligourethane, and C) an additive, in particular a solvent, 5-90% by weight, provided that A) + B) + C) in total 10
Pigment preparation according to claim 1, which contains 0% by weight. 3. A) 5-30% by weight of organic pigments, B) 5-98% by weight of oligourethanes, and C) additives, especially 8-90% by weight of solvents, provided that A) + B) + C) in total. 10
Pigment preparation according to claim 1, which contains 0% by weight. 4. A) 2-80% by weight of an inorganic pigment, B) 5-98% by weight of an oligourethane, and C) an additive, in particular a solvent, 5-90% by weight, provided that A) + B) + C) in total 10
Pigment preparation according to claim 1, which contains 0% by weight. 5. A) 10-65% by weight of inorganic pigments, B) 5-98% by weight of oligourethanes, and C) additives, especially solvents 8-90%.
% by weight, provided that A) + B) + C) totals 1
2. Pigment preparation according to claim 1, which contains 0.00% by weight. 6. The pigment preparation according to any one of claims 1 to 5, wherein the oligourethane has a molecular weight of 5,000 to 50,000. 7. The molecular weight of oligourethane is 15,000 to 40,000
A pigment preparation according to any one of claims 1 to 5. 8. The pigment preparation according to any one of claims 1 to 7, wherein the oligourethane has a sterically hindered isocyanate group. 9. The pigment preparation according to any one of claims 1 to 8, wherein the oligourethane has a protected isocyanate group. 10. Use of the pigment preparation according to any one of claims 1 to 9 for coloring leather and finishing agents for leather cloth.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3914568.9 | 1989-05-03 | ||
DE3914568A DE3914568A1 (en) | 1989-05-03 | 1989-05-03 | PIGMENT PREPARATIONS |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH036272A true JPH036272A (en) | 1991-01-11 |
Family
ID=6379979
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2115334A Pending JPH036272A (en) | 1989-05-03 | 1990-05-02 | Pigment preparation |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0395955B1 (en) |
JP (1) | JPH036272A (en) |
CA (1) | CA2015824A1 (en) |
DD (1) | DD298418A5 (en) |
DE (2) | DE3914568A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012051982A (en) * | 2010-08-31 | 2012-03-15 | Auto Kagaku Kogyo Kk | Colorant composition, method of producing the colorant composition, coloring method using the colorant composition, and method of producing sealing material |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5770651A (en) * | 1991-04-16 | 1998-06-23 | Bayer Aktiengesellschaft | Use of oligourethanes as formulating agents for aqueous pigment preparations |
DE4112326A1 (en) * | 1991-04-16 | 1992-10-22 | Bayer Ag | OLIGOURETHANE (UREA) AS A PIGMENT BINDING AGENT IN ORGANIC MEDIUM |
DE19636898A1 (en) * | 1996-09-11 | 1998-03-12 | Bayer Ag | Pigment preparations |
WO1999052966A1 (en) * | 1998-04-15 | 1999-10-21 | Mikuni Shikiso Kabushiki Kaisha | Aqueous pigment dispersion, process for producing the same, and water-based ink comprising the same |
CN104962136B (en) * | 2015-07-03 | 2017-08-11 | 苏州世名科技股份有限公司 | A kind of aqueous carbon black pigment mill base coloured for synthetic leather |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3625605A1 (en) * | 1986-07-29 | 1988-02-11 | Hoechst Ag | AQUEOUS PIGMENT PREPARATIONS AND THEIR USE |
DK191789A (en) * | 1988-05-05 | 1989-11-06 | Sun Chemical Corp | SEMIPOLARY HYPERDISPERSANT TO MAKE HIGH CONCENTRATED DISPERSIONS OF PIGMENTS |
-
1989
- 1989-05-03 DE DE3914568A patent/DE3914568A1/en not_active Withdrawn
-
1990
- 1990-04-20 EP EP90107528A patent/EP0395955B1/en not_active Expired - Lifetime
- 1990-04-20 DE DE90107528T patent/DE59004652D1/en not_active Expired - Fee Related
- 1990-05-01 CA CA002015824A patent/CA2015824A1/en not_active Abandoned
- 1990-05-02 DD DD90340309A patent/DD298418A5/en not_active IP Right Cessation
- 1990-05-02 JP JP2115334A patent/JPH036272A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012051982A (en) * | 2010-08-31 | 2012-03-15 | Auto Kagaku Kogyo Kk | Colorant composition, method of producing the colorant composition, coloring method using the colorant composition, and method of producing sealing material |
Also Published As
Publication number | Publication date |
---|---|
EP0395955A1 (en) | 1990-11-07 |
CA2015824A1 (en) | 1990-11-03 |
DD298418A5 (en) | 1992-02-20 |
EP0395955B1 (en) | 1994-02-23 |
DE59004652D1 (en) | 1994-03-31 |
DE3914568A1 (en) | 1990-11-08 |
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